Manufacture of aminodiphenylether sulphonic acids



Patented Feb. 2, 1943 MANUFACTURE OF ADIINODIPHENYLETHER SULPHONIC ACIDS Henry Martin, Basel, and Hans Heinrich Zaes'l'in, Itiehen, near Basel, Switzerland, assignors to the firm J. R. Geigy A. G., Basel, Switzerland No Drawing. Application April 27,1940, Serial N0. 332,104. In Switzerland May 16, 1939 10 Claims.

This invention relates to an improvement in or modification of the invention set forth in the U. S. patent application Ser. No. 309,292, filed December 14, 1939, assigned to th same assignee as the present one.

That invention concerns a process for the production of aminoaryl sulphonic acid derivatives by reacting a monoamino sulphonic acid of the general formula -NHz X l son J 3 wherein X represents a divalent atom (such as or S) or a divalent atom group (such as S0, S02, CH2, CO, NH, NH-CO-NH), either with an aromatic, araliphatic or high molecular aliphatic monoacylating agent; or with any polyacylating agent; or with an aralkylating agent or an alkylating agent containing a high molecular alkyl radical which may be substituted or contain a hetero atom or hetero atom group in the alkyl part; or "with the aforesaid aralkylating agent or alkylating agent followed by the action of any acylating agent; and introducing at least one halogen atom into the final compound, either by usinga halogenated reaction component in the reaction or by halogenating the product of the said reaction.

All the final compounds produced according to the above said U. S. patent application are thus halogen containing ones, and are all notably suitable formoth-proofing wool, furs, feathers, hair, textile fabrics or the like, made last to light, washing and fulling by the acid dyeing method.

It'is very surprising now to find that halogenfree, colorless, acylated aminodiphenylether sulthe same way as acid dyestufis fromthepaci'd bath phonic acids containing a, high molecular acyl radical and a very definite alkyl substitution can be used. as moth-proofing agents. These products can be obtained by acylation of halogen-free aminodiphenylether sulphonic acids.

As halogen-free amino aryl sulphonic acids for use according to the present improvement or modification, only nuclear alkylated compounds so substituted by one or more alkyl groups, that if a single methyl group be present alone, it is The aminoaryl sulphonic acids thus defined are reacted with high molecular aliphatic or araliphatic acylating agents which are so selected 5 that no halogen will be present in the final product. For this purpose capric acid, palm nut fatty acid, lauric acid, stearic acid, palmitic acid, myristic acid, oleic acid, naphthenic acid, fencholic acid, resin acid or cinnamic acid are suitable examples. It should be understood, however, that the functional derivatives of these acylating agents, such as the halides. esters or anhydrides, may be used.

Halogen-free, moth-proofing agents containing sulphonic acidroups have previously been suggested, produced in various ways. There may be mentioned hydroxytriarylmethanes containing sulphonic acid groups, produced by condensation of p-alkylated phenols and aldehyde sulphonic acids and so forth. These products in addition to having alow light fastness are'iast neither to fulling nor to washing. sulphonicacid groups-containing, halogen-free condensation products from alkylated phenols and derivatives of isatin do not acquire the strength possessed by halogen-free condensation products produced according to the present invention. Further condensation products of aldehyde sulphonic acids and partly halogen-free mercaptans have been proposed and also recommended as moth-proofing agents.

The following table shows that none of the above mentioned compounds is capable of producing such good or valuable properties as the halogen-free condensation products produced according to this invention, from aminoary sulphonic acids and aliphatic or araliphatic acylating agents as herein defined.

Prescription for application and test The compounds are applied to Wool fabric in and each is exposed to 10 moth larvae.

Table Fabric treated with 2 Fabric treated with 6 percent moth proofpercent moth-proof- Compound ing agent mg agent Dried Washed Fulled Dried Washed Fullcd l I I 1 1 I No. 5 (according to present application) No. 6 (accordiug to present app o Indicates protected; Indicates insufficient protection against being moth eaten.

Compound No. 1

Compound No. 2

Compound No. 3

I CHOSOQH Compound No. 4

soan

Compound No. 5

s O Na Compound No. 6

S O3N8 Example 1 I 30 parts of 4-amino-4'-methyl-1:1'-diphenyland then stirring takes place at 30-40 C. until Then treatno further free amine is traceable.

ment is carried out with soda solution and the pyridine is distilled ofi with steam. The residue is allowed to cool, is acidified with hydrochloric acid and finally any fatty acid still present is The condensation extracted from the mixture. product corresponds with the formula S OaNa Example 2 28 parts of 4-amino-2'-methy1-5-isopropyl- 1 1'-diphenylether-2-sulphonic acid (produced from p-chloronitro-benzene-su1phonic acid and thymol, alkali salt, and subsequent reduction) are suspended in 200 parts by volume of dry pyridine, at ordinary temperature 15 parts of lauroyl chloride are added in drops and then stirring takes place at 30-40 C. until no further non-converted amine is present. The Working up is effected as above. The condensation product corresponds with the formula CH S OgNll CH3 CH3 Instead of the amino-diphenylether sulphonic acid mentioned in the above examples there may be used other halogen-free compounds, for example:

2 amino 3:5-dimethyl-1:1-diphenylether-4- sulphonic acid,

4 amino-3-methyl-6'-lsopropyl-1:1-diphenylether-2-sulphonic acid,

2 amino -3'-methyl-6'-isopropyl-1:1'-diphenyletherl-sulphonic acid,

2 amino 4'- amyl 1:.1'- diphenylether 4-su1- phonic acid,

2 amino 4- amyl 1:1'-diphenylether 2-sulphonic acid,

4 amino 4- amyl 1:1'-diphenylether 2'-sulphonic acid,

2 amino 4"- tert.-butyl-1:1'-diphenylether-2'- sulphonic acid,

2 amino 4-isohexy1-6-methyl-l:1'-diphenylether-2'-sulphonic acid.

All these compounds are made according to known methods by reacting an alkali phenolate, for example the sodium salt of 3:5-dimethyl-1 hydroxylbenzene with a halogennitrobenzene body, containing exchangeable halogen, such as 4-chloronitrobenzene-3-sulphonic acid and subsequent reduction of the nitrodiphenylether obtained. The sulphonic acid group may also be introduced by after-sulphonation.

What we claim is:

1. A process for the manufacture of mothproofing agents, comprising acylating 4-amino- 4'-methyl-1:1-diphenylether 2 sulphonic acid with lauroylchloride.

2. A process for the manufacture of a mothproofing agent, comprising acylating 4-amino- 4'-amyl 1:1-diphenylether 2 sulphonic acid with lauroylchloride.

3. A process for the manufacture of a mothproofing agent, comprising acylating 4-amino- 2'-'m ethy*l 5'-isopropyl 1:1- diphenylether-Z- sulphonic acid with lauroylchloride.

4. The alkyl substituted, halogen-free aminodiphenylether sulphonic acid of the formula:

5. The alkyl substituted, halogen-free aminodiphenylether sulphonic acid of the formula:

NHCOC11H::

6. The alkyl substituted, halogen-free aminodiphenylether sulphonic acid of the formula:

QOQNH-C O-CuHas 33 s 03H CH3 CH3 7. A process for the manufacture of mothproofing agents comprising acylating a halogeniree aminodiphenylether' sulphonic acid containing as substituents of the phenyl nuclei at least one alkyl group selected from the group consisting of alkyl radicals of 1 to 6 carbon atoms, with a high molecular aliphatic acylating agent to obtain an alkylsubstituted, halogenfree aminodiphenylether sulphonic acid substituted in its amino group by a high molecular acyl radical.

8. A process for the manufacture of mothproofing agents comprising acylating a halogenfree aminodiphenylether sulphonic acid containing as substituents of the phenyl nuclei at least one alkyl group selected from the group consisting of alkyl radicals of .1 to 6 carbon atoms, with a lauroyl halide to obtain an alkylsubstituted, halogen-free. aminodiphenylether sulphonic acid substituted in its amino group by a high molecular acyl radical.

9. The new halogen-free aminodiphenylether sulphonic acids containing as substituents of the phenyl nuclei at least one alkyl group selected from the group consisting of alkyl radicals of 1 to 6 carbon atoms substituted in their amino group by a high molecular aliphatic acyl radical and being valuable moth-proofing agents.

10. The new halogen-free aminodiphenylether sulphonic acids containing as substituents of the phenyl nuclei at least one alkyl group selected from the group consisting of alkyl radicals of 1 to 6 carbon atoms substituted in their amino group by the lauroyl radical and being valuable moth-proofing agents.

HENRY MARTIN. HANS HEINRICH ZAESLIN. 

